CN107964109A - A kind of delustring black polyamide thin film preparation method - Google Patents
A kind of delustring black polyamide thin film preparation method Download PDFInfo
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- CN107964109A CN107964109A CN201711352464.9A CN201711352464A CN107964109A CN 107964109 A CN107964109 A CN 107964109A CN 201711352464 A CN201711352464 A CN 201711352464A CN 107964109 A CN107964109 A CN 107964109A
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- C08J5/18—Manufacture of films or sheets
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The present invention is a kind of delustring black polyamide thin film preparation method, key step:Ith, polyamic acid resin solution is routinely prepared.IIth, black paste is prepared, black pigment amount is 2~20wt% of polyamic acid resin solution solid content M.IIIth, delustring agent dispersing liquid is prepared, delustring dosage is 2~20wt% of M.IVth, black polyamic acid resin solution is prepared, above-mentioned polyamic acid resin solution, black paste and delustring agent dispersing liquid blending and stirring, defoam spare.Vth, black polyamic acid solution routinely salivate, stretch, imidization and sizing, and after biaxial tension, or after imidization, or after sizing, 640 DEG C~800 DEG C are carried out to film, continues the high temperature surface treatment of 5s~120s, delustring black polyamide thin film is made.The black pigment and delustering agent average grain diameter of the present invention is moderate, increases high temperature surface treatment in resin solution salivates forming process, gained film light transmittance, glossiness and physico mechanical characteristic have clear improvement.
Description
Technical field
The present invention relates to Kapton manufacturing technology, is specially a kind of delustring black polyamide thin film preparation side
Method.
Background technology
Flexible printed wiring board (FPC) is widely used in 3C Product, optical lens module, liquid crystal display (LCD) module
And the product such as solar cell, and Kapton (Polyimide Film, abbreviation PI film) is commonly used for its base material or covering
Membrane material, since traditional PI film is respectively provided with high surface flatness in application process, film surface reflects most incident ray
And produce high gloss.The dazzle or astigmatism that the film surface of high gloss is produced there are light reflection, cause the uncomfortable of vision, when long
Between watch when easily make eye fatigue.Especially there is the high gloss PI films polyamides Asia of the colors such as black, white, blueness, red
Amine film, influence of the reflected light that its surface produces to vision are more notable.
On the other hand, when the larger and transparent higher PI films of surface gloss are applied to FPC, the circuit design point of FPC
Cloth is easy to understand and plagiarized by the same trade.
So the existing market demand possesses the PI films of the characteristics such as low-luster, low light transmission and high insulation resistance.Low-luster
The high insulation resistance and low light transmission of black PI films can protect internal circuit design, while component facade can be made to have more texture and U.S.
See.
The production technology of Kapton is using the polyamic acid resin solution by polycondensation reaction synthesis as original at present
Material, on slobbering machine salivation obtain the polyamic acid thick film with self-supporting, then by heating stretching, imidization, sizing at
Reason obtains Kapton.Obtain having concurrently the Kapton of low-luster, low light transmission and high insulation resistance, poly-
Must be added in imide membrane preparation process in colour additive (such as：Colorant, dyestuff etc.) and delustering agent.General technique is
Colour additive is used to reduce the light transmittance of Kapton, or addition delustering agent causes Kapton surface shape
Into concave-convex micro-structure to reduce the glossiness of Kapton.
The delustering agent of micron-level particle size is generally used in the prior art, because of the filtration system filter core aperture of existing extrusion die
Smaller, delustering agent frequently results in filtration system and blocks during extrusion salivates, and can not realize the serialization film of long period.
If the foreign matters such as the impurity that increase filtration system filter core aperture is be easy to cause in resin solution, gel are embedded in film again, cause thin
Film surface quality declines.
In black polyamide thin film manufacturing process, when inorganic particle (delustering agent) or carbon powder material (being in colour additive)
Particle diameter is too big or too small, and or adding too much or it is too low can be caused for the physical property of Kapton it is undesirable
Influence.If the particle diameter of inorganic particle or carbon powder material is larger, manufactured film surface is excessively coarse, is not suitable for electronic product
In；If the particle diameter of inorganic particle or carbon powder material is smaller, powder clustering phenomena is easily produced, causes additive in film to disperse
Non-uniform problem, and the operation of manufacturing process is difficult to control.It is dispersed in Kapton to influence additive, removes
The particle diameter of inorganic particle or carbon powder material, also has the content of inorganic particle or carbon powder material.If in film inorganic particle or
The content of carbon powder material is very few, and film glossiness and light transmittance can not just reduce and reach requirement.And content it is larger when, can equally produce
Raw additive disperses non-uniform problem；A large amount of addition delustering agents also result in Kapton performance degradation, easy embrittlement,
And a large amount of additives easily occur sedimentation and reunite in polyamic acid resin, can also increase the production cost of film.
The material of delustering agent can be divided into inorganic compound and organic compound.Wherein inorganic compound includes silica, oxygen
Change aluminium, calcium carbonate, barium sulfate, titanium dioxide etc., inorganic particulate has higher bulk density, if adding substantial amounts of inorganic particulate
It is may result in polyimide matrix to reunite and disperse inequality, so that the uniformity of film electrical insulating property is reduced, it is unfavorable
In subsequent applications.And the organic compound for being used for delustering agent includes poly- carbonic acid vinegar (PC), polystyrene (PS), polymethylacrylic acid
Methyl esters (PMMA), polyethylene (PE), polypropylene (PP), two vinegar of poly terephthalic acid second (PET), epoxy resin etc..Due to poly-
In the preparation process of imide membrane, chemical conversion temperature must be more than 250 DEG C, but above-mentioned organic compound can not all bear 250
DEG C or higher temperature.Made an addition to when using such organic compound as delustering agent in Kapton, film can occur
Crackle or hole, or because melt it is uneven produce color inconsistent patch the defects of.
At present, the main production technology of delustring black PI films is divided into two classes:One kind is to add black pigment in PI resins
With delustering agent filler, then there is the PI films of low-transmittance and low-luster by chemical imidization or hot imidization, synthesis,
This method is easy to operate, and positive effect, but due to the addition of mass filler, significantly reduces the mechanical property of PI films
Energy；Another kind of is one layer of PI film containing black pigment and photoextinction of coating on the single or double of PI basement membranes.Although this
Kind method can preferably make Kapton that desirable black effect be presented, and can ensure that Kapton is certain
Mechanical performance, but the black resin being additionally coated with would generally increase manufacturing process and cost, and to Kapton
Matter adversely affects.In addition, also Kapton can be caused to be exposed to hot adverse circumstance because resin coated layer heat resistance is poor
When performance degradation easily occurs.Existing many patent applications in relation to manufacturing low gloss black polyamide thin film, but because of manufacture
Complex process, production control accuracy requirement is higher and manufactures the defects such as cost height, it is difficult to implements.
Such as Chinese invention patent CN104742461A " the double-deck polyimide films and its system of low-luster of application in 2015
Make method " blending is inserted between levels polyimide film there is black pigment and form recess and hole in the thickness direction of film
The polyimide film in hole, obtains having high screening optical activity, the double-deck Kapton of low-luster concurrently.The China of application in 2015
Patent of invention CN 104830058A " polyimide film of low-k and low-luster and preparation method thereof ", film main structure
It is monofilm or multilayer for the fluoro containing polymers of polyimides, the carbon black of 0.5wt% to 5wt% and 15wt% to 40wt%
Film.Chinese invention patent " delustering agent, the polyimides containing the delustering agent being made of polyimides powder of application in 2012
Film and preparation method thereof " is disclosed the organic matting agent that polyimides powder is formed being uniformly distributed in Kapton and made
The Kapton of good film characteristics and low-luster must be had concurrently.The Chinese invention patent CN of application in 2012
103561953 A " polyimide film " have bag on the single or double of the polyimide layer (A) containing black organic pigment
Containing inorganic or organic filler polyimide layer (B), electrical insulating property, the electricity of the film are excellent in reliability.
The content of the invention
The purpose of the present invention is designing a kind of delustring black polyamide thin film preparation method, using general with such film
The delustering agent used prepares polyamic acid resin solution compared to the less inorganic filler delustering agent of average grain diameter, is salivated into
Film, high temperature surface treatment is also carried out during biaxial tension, high temperature imidization and heat treatment is carried out.Polyamides obtained by this law
Imines film product glossiness and light transmittance substantially reduce, and film roll profile pattern increase, appearance substantially improves.
A kind of delustring black polyamide thin film preparation method provided by the invention, including following key step:
Ith, the preparation of polyamic acid resin solution
Prepare polyamic acid resin solution according to a conventional method, in an inert atmosphere, control synthetic system temperature for 12 DEG C~
Aromatic diamine is added into solvent under conditions of 75 DEG C and be stirred dissolving, after aromatic diamine is completely dissolved, divide 3~8 times at the uniform velocity
It is (0.9~1.1) to add with aromatic diamine molar ratio：1 aromatic dianhydride, and stirred with 120r/ minutes~1200r/ minutes,
Synthesize to obtain polyamic acid resin solution through 3~24h of polycondensation reaction.
In view of cost, inert atmosphere is generally realized with nitrogen.
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The polyamic acid resin solution that the dosage control of the aromatic diamine, aromatic dianhydride and solvent is formed for this step
In the ratio of solid content M be 10wt%~50wt%.
The aromatic diamine is 3,4'- diaminodiphenyl ethers, 1,3- bis--(4- amino-benzene oxygens) benzene, 4,4'- diaminourea two
Phenylate (4,4'-ODA), 1,3- diaminobenzenes, 2,2'- bis- (trifluoromethyl) benzidine, 4,4'- benzidines and p-phenylenediamine
(p-PDA) any one in or any a variety of combination.
The aromatic dianhydride is Pyromellitic Acid diacid (PMDA), 3,3', and 4,4'- biphenyl four completes acid diacid acid anhydride
(BPDA), 2,2', 3,3'- biphenyl four completes acid diacid acid anhydride (BPDA), diphenyl ether tetraformic dicarboxylic anhydride (ODPA), Benzophenone and completes acid two
Double (the 3,4- dicarboxylic acids phenyl) hexafluoropropane dianhydrides (6FDA) of acid anhydrides (BTDA), 2,2-, the double phthalic anhydrides of 4,4'- oxygen
(ODPA), 3,4,3', 4'- diphenyl thio-ether tetrformate dianhydride (3,4,3', 4'-TDPA), 2,3,2', 3'- diphenyl thio-ether tetrformates
It is any one in dianhydride (2,3,2', 3'-TDPA) and 2,3,3', 4'- diphenyl thio-ether tetrformate dianhydride (2,3,3', 4'-TDPA)
Kind or any a variety of combination.
IIth, prepared by black paste
Take black pigment to add in solvent to be mixed evenly to obtain black paste；The amount for adding black pigment is step I
2wt%~20wt% of solid content M in the polyamic acid resin solution, 0.01~0.8 μ of black pigment average grain diameter
m。
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The solvent dosage control of the black paste be black pigment content ratio in black paste be 10wt%~
30wt%.
The amount of the black pigment added is preferably 6wt%~10wt% of M.
The average grain diameter for the black pigment that preferred version is added for O.015 μm~0.4 μm, be preferably average grain diameter O.02
μm~0.1 μm.If the particle diameter of black pigment is smaller, the phenomenon of aggregation is easily produced, causes to disperse non-uniform ask in the film
Topic, and be difficult to control in process operations.If the particle diameter of black pigment is larger, manufactured film surface is excessively coarse, does not apply to
In electronic product；If the additive amount of filler is too small, the same light-proofness effect that suppresses reduces；If excessive, polyamides Asia is damaged
Amine film physical property.
The mixing after black pigment is added in the solvent first to mix shear agitation, afterwards high speed dispersion mulser
Emulsification pretreatment processing, then handled through high pressure homogenizing, black paste is made.
IIIth, prepared by delustring agent dispersing liquid
Cancel after photo etching is added in solvent and be mixed evenly to obtain delustring agent dispersing liquid, the delustring dosage of addition is step
2wt%~20wt% of solid content M in the I polyamic acid resin solution, the delustering agent average grain diameter are 0.01~0.8
μm。
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides
(DMAC), N, N'- dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), tetramethyl sulfone, N,
N'- dimethyl-N, N'- acrylic urea (DMPU), N, any one in N dialkyl group Carboxylamides or any a variety of combination.
The delustering agent is any one in silica, polyimides, aluminium oxide and titanium dioxide or any a variety of
Combination.
The solvent dosage control of the delustring agent dispersing liquid is that the dulling agent content ratio in delustring agent dispersing liquid is
10wt%~30wt%.
Preferred version is 8wt%~12wt% that the amount of the delustering agent added is M.
The delustering agent average grain diameter that preferred version is added for O.05 μm~0.6 μm, the delustering agent preferably added is averaged
Particle diameter O.08 μm~0.3 μm.
If the average grain diameter of delustering agent is too small relative to Kapton thickness to be prepared, suppress glossiness effect
Reduce；If excessive, can not be sufficiently secured within Kapton.It is same to suppress gloss if the additive amount of filler is too small
Spending effect reduces；If excessive, Kapton physical property is damaged.
The mixing added in the solvent after delustering agent is mixing shear agitation to be first, afterwards high speed dispersion mulser
Emulsification pretreatment processing, then ground machine milled processed, and further carry out ultrasonic disperse processing and delustring agent dispersing liquid is made.
The step I prepares polyamic acid resin solution, step II prepares black paste and step III prepares delustering agent
Solvent used in dispersion liquid is identical.
IVth, prepared by black polyamic acid resin solution
Take polyamic acid resin solution obtained by step I, black paste obtained by step II and the delustering agent obtained by step III
Dispersion liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare；
Vth, prepared by delustring black polyamide thin film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, and thickness 20~
520 μm, the then dry solvent for removing 85wt%~40wt% at 100~250 DEG C, obtain with can self-supporting polyamides
Amino acid film, gained polyamide acid film is peeled off from ring steel belt and is delivered to 0.8~2.2 times of progress on biaxial orientation stretching machine in length and breadth
Stretching, 180 DEG C~500 DEG C high temperature imidization processing, after last 180 DEG C~360 DEG C sizings, winding, is made 2.5~50 μm of thickness
Delustring black polyamide thin film.
After biaxial tension, either after imidization processing or after sizing, it is 640 DEG C that a temperature is carried out to film
~800 DEG C, the high temperature that the duration is 5s~120s surface treatment.
The high temperature surface treatment, makes the delustering agent inside film, black pigment carry out surface migration, wriggling and occurs equal
Even aggregation (particularly delustering agent inorganic filler aggregation is obvious and uniform), filler is coarse by self assembly behavior generation (micron order)
And irregular molding modified surface, reduce film glossiness.If temperature is too low when high temperature is surface-treated, extinction effect is unknown
It is aobvious；Temperature is excessive, be easy to cause film degradation, and film physical property reduces；High temperature surface treatment its too short extinction effect of time is same
Unobvious, processing time is long, be easy to cause film degradation, and film physical property reduces.
Preferred version is that the temperature of the high temperature surface treatment is 650 DEG C~750 DEG C, and the time is 10s~90s.
Preferred solution is that the temperature of the high temperature surface treatment is 660 DEG C~700 DEG C, and the time is 15s~60s.
Film is in tensioning state during the high temperature surface treatment, and tensioning draw ratio is 1.0~1.6, i.e., film, which is in, draws
Stretch and the high temperature surface treatment is carried out under state.
When the high temperature surface treatment is different from high temperature imidization or sizing in existing Kapton manufacturing process
High-temperature process, the surface treatment of increased high temperature, the temperature of high temperature of the invention surface treatment is far above current high temperature imidization
500 DEG C of maximum temperature and sizing 360 DEG C of maximum temperature, TRANSIENT HIGH TEMPERATURE is to reduce the special place of film surface glossiness
Science and engineering skill.
Compared with prior art, it is the advantages of a kind of delustring black polyamide thin film preparation method of the invention：1st, it is conventional
Delustering agent median particle size is micron order, and delustering agent granularity of the invention is only 0.01~0.8 μm, and film passes through short time high temperature surface
Processing, makes delustering agent, black pigment reunite, reduces film surface glossiness；2nd, prepared delustring black polyamide thin film
Visible light transmittance rate is less than 0.1%, 60 ° of gloss value ＜ 25, elongation ＞ 60%, tensile strength >=230MPa, springform
＞ 3.5GPa are measured, and maintain the insulation performance and mechanical property of Kapton itself；3rd, prepared delustring black polyamides
Imines film has shading, photoextinction, and because the processing on high temperature surface enhances the tear resistance of film；4th, high temperature surface
Processing also eliminates film surface striped and stress in thin films, hence it is evident that improves Kapton product surface quality；5th, increased
High temperature process of surface treatment, can be in the existing imidization processing in Kapton manufacturing process or heat treatment
Increase high temperature section in baking oven to realize, debugging is easy, and can ensure that producing continuous, technique is simple and convenient to operate；6th, this method
Prepared delustring black polyamide thin film is suitable for the basement membrane or cover layer, electronic tag basement membrane of flexible print circuit board
Deng.
Embodiment
Embodiment 1
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled as 12 DEG C, to 45kg N, N'- dimethylacetylamides (DMAC) solvent
Middle addition 2.39kg aromatic diamines 4,4'- diaminodiphenyl ethers (4,4'-ODA) are stirred dissolving, and 4,4'-ODA are completely dissolved
Afterwards, it is 1 to divide 8 at the uniform velocity addition and aromatic diamine molar ratios:1 2.61kg aromatic dianhydride Pyromellitic Acid diacid (PMDA),
And stirred with 1200r/ minutes, synthesize to obtain solid content M=5kg through polycondensation reaction 12h, i.e. solid content ratio is the poly- of 10wt%
Amic acid resin solution；
IIth, prepared by black paste
The 20wt% of the solid content M in polyamic acid resin solution as obtained by step I takes carbon black 1kg to add solvent N,
It is mixed evenly to obtain the black paste of content of carbon black 30% in N'- dimethylacetylamides (DMAC) 2kg；This example carbon black is averaged
0.01 μm of particle diameter.
The black pigment of this step can also use black titanium, bone black (bone black), Cyanine Black (cyanine black), second
Acetylene black, lampblack, graphite, iron oxide black, nigrosine and Hua Jing it is black in any one or any a variety of combination.
The mixing added in this example N, N'- dimethylacetylamide (DMAC) solvent after black pigment carbon black exists to be first
Shear agitation 30 minutes is mixed under the conditions of 120r/ minutes, after through high speed dispersion mulser emulsification pretreatment processing in 3600r/ minute
240 minutes, then through the high-pressure homogeneous processing of high pressure homogenizer 180MPa 30 minutes, black paste is made.
IIIth, prepared by delustring agent dispersing liquid
The 2wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching silica 0.1kg
It is mixed evenly to obtain dioxide-containing silica ratio 20% after adding in solvent N, N'- dimethylacetylamide (DMAC) 0.5kg
Delustring agent dispersing liquid, this example silica average grain diameter be 0.8 μm.
The delustering agent of this step can also use any one in polyimides, aluminium oxide and titanium dioxide or any a variety of
Combination.
The mixing added in this example solvent N, N'- dimethylacetylamide (DMAC) after delustering agent silica exists to be first
Shear agitation 30 minutes is mixed under the conditions of 1200r/ minutes, after through high speed dispersion mulser emulsification pretreatment processing in 1200r/ minute
30 minutes, then ground machine milled processed 30 minutes, and further carry out that delustering agent point is made after ultrasonic disperse is handled 240 minutes
Dispersion liquid.
IVth, prepared by black polyamic acid resin solution
Take polyamic acid resin solution obtained by step I, black paste, the delustering agent of step III gained disperse obtained by step II
Liquid is blended, and black polyamic acid resin solution is made, and defoam spare.
Vth, prepared by delustring black polyamide thin film
Black polyamic acid solution prepared by step IV is coated on ring steel belt by extrusion molding mould, thickness 20
μm, the dry solvent for removing 40wt% at 100 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamide
Sorrel is peeled off and is delivered to from ring steel belt carries out 2.2 times of stretchings in length and breadth on biaxial orientation stretching machine, at 500 DEG C of high temperature imidizations
Reason, this example carry out film after imidization processing the high temperature that temperature is 640 DEG C, the duration is 5s and are surface-treated, then
360 DEG C of sizing is carried out, is finally wound, the delustring black polyamide thin film of 2.5 μm of thickness is made.
Embodiment 2
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, to control synthetic system temperature be 22 DEG C, to 37.5kg N, in N'- dialkyl group Carboxylamide solvents
Add 6.38kg aromatic diamines 2, double (trifluoromethyl) benzidine of 2'- are stirred dissolving, after it is completely dissolved, divide 3 times it is even
It is 0.98 that speed, which is added with aromatic diamine molar ratio,:1 5.99kg aromatic dianhydrides 3,3', 4,4'- biphenyl four completes acid diacid acid anhydride
(BPDA), and with 1000r/ minutes stir, synthesize to obtain solid content M=12.4kg through polycondensation reaction 8h, i.e. solid content ratio is
The polyamic acid resin solution of 25wt%；
IIth, prepared by black paste
The 16wt% of the solid content M in polyamic acid resin solution as obtained by step I takes iron black 2kg to add solvent N,
It is mixed evenly to obtain the black paste of iron black content 10% in N'- dimethyl sulfoxides (DMSO) 18kg；The iron black average grain of this example
0.8 μm of footpath.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 20wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching silica 2.5kg
It is mixed evenly to obtain disappearing for dioxide-containing silica ratio 30% after adding in solvent N-methyl pyrilidone (NMP) 5.8kg
Photo etching dispersion liquid, this example silica average grain diameter are 0.01 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by delustring black polyamide thin film
By extrusion molding mould coated on ring steel belt, thickness is black polyamic acid solution prepared by step IV
520 μm, the dry solvent for removing 85wt% at 250 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamides
Amino acid film is peeled off and is delivered to from ring steel belt carries out 0.8 times of stretching in length and breadth on biaxial orientation stretching machine.This example is after biaxial tension
The high temperature that a temperature is 800 DEG C, the duration is 120s is carried out to film to be surface-treated.180 DEG C of high temperature imines are carried out afterwards
Change is handled, then after carrying out 180 DEG C of sizing, winding, and the delustring black polyamide thin film of 50 μm of thickness is made.
Embodiment 3
Ith, the preparation of polyamic acid resin solution
In nitrogen atmosphere, synthetic system temperature is controlled to add for 50 DEG C into 25kg 1-methyl-2-pyrrolidinones (NMP) solvent
Enter 7.92kg aromatic diamines 3,4'- diaminodiphenyl ethers (3,4'-ODA) are stirred dissolving, after it is completely dissolved, divide 5 times
It is 1.02 at the uniform velocity to add with aromatic diamine molar ratio:1 17.23kg aromatic dianhydrides 2, double (3, the 4- dicarboxylic acids phenyl) hexafluoros of 2-
Propane dianhydride (6FDA), and stirred with 1000r/ minutes, synthesize to obtain solid content M=25.15kg through polycondensation reaction 8h, i.e., contain admittedly
Amount ratio is the polyamic acid resin solution of 50wt%；
IIth, prepared by black paste
The 4wt% of the solid content M in polyamic acid resin solution as obtained by step I takes acetylene black 1kg to add solvent N-
It is mixed evenly to obtain the black paste of acetylene black content 15% in methyl pyrrolidone (NMP) 5.6kg；This example acetylene black is put down
Equal 0.02 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 16wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching aluminium oxide 4.04kg
The delustering agent for being mixed evenly to obtain alumina content ratio 20% after adding in solvent dimethyl sulfoxide (DMSO) 16kg disperses
Liquid, this example aluminium oxide average grain diameter are 0.3 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by delustring black polyamide thin film
By extrusion molding mould coated on ring steel belt, thickness is black polyamic acid solution prepared by step IV
250 μm, the dry solvent for removing 70wt% at 180 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamides
Amino acid film is peeled off and is delivered to from ring steel belt carries out 1.2 times of stretchings in length and breadth on biaxial orientation stretching machine, then carry out 380 DEG C of high temperature
Imidization handle, then carry out 250 DEG C sizing, this example after sizing, to film carry out a temperature be 700 DEG C, the duration be
The high temperature surface treatment of 60s.Finally wind, the delustring black polyamide thin film of 25 μm of thickness is made.
Embodiment 4
Ith, the preparation of polyamic acid resin solution
In argon gas gas atmosphere, synthetic system temperature is controlled as 60 DEG C, to 42.5kg N, N'- dimethyl-N, N'- acrylic
2.22kg aromatic diamines p-phenylenediamine (p-PDA) is added in urea (DMPU) solvent and is stirred dissolving, after p-PDA is completely dissolved,
It is 1.1 to divide 5 at the uniform velocity addition and aromatic diamine molar ratios:1 5.48kg aromatic dianhydrides biphenyl four completes acid diacid acid anhydride (BPDA),
And stirred with 800r/ minutes, synthesize to obtain solid content M=7.70kg through polycondensation reaction 3h, i.e. solid content ratio is 15wt%'s
Polyamic acid resin solution；
IIth, prepared by black paste
The 6wt% of the solid content M in polyamic acid resin solution as obtained by step I takes the black 0.47kg of titanium to add solvent N,
It is mixed evenly to obtain the black paste of the black content 10% of titanium in N'- dialkyl group Carboxylamides 4.23kg；This example titanium is black average
0.1 μm of particle diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 5wt% of the solid content M in polyamic acid resin solution as obtained by step I takes TITANIUM DIOXIDE DELUSTRANT 0.39kg
It is mixed evenly to obtain disappearing for content of titanium dioxide ratio 12% after adding in solvent N, N'- dialkyl group Carboxylamide 2.86kg
Photo etching dispersion liquid, this example titanium dioxide average grain diameter are 0.08 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by delustring black polyamide thin film
By extrusion molding mould coated on ring steel belt, thickness is black polyamic acid solution prepared by step IV
360 μm, the dry solvent for removing 60wt% at 150 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamides
Amino acid film peeled off from ring steel belt and be delivered in length and breadth on biaxial orientation stretching machine carry out 1.6 times stretching, this example after biaxial tension,
Carry out the high temperature that a temperature is 750 DEG C, the duration is 15s to film to be surface-treated, film is in tensioning state at this time, draws
Stretch than for 1.4.Then 450 DEG C of high temperature imidization processing is carried out, then carries out 300 DEG C of sizing, finally, winding, is made thickness
36 μm of delustring black polyamide thin film.
Embodiment 5
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, control synthetic system temperature to be 15 DEG C, to 40kg N, add in N'- Dimethyl Asian Maple (DMSO) solvent
Enter 2.49kg aromatic diamines p-phenylenediamine (p-PDA) and be stirred dissolving, after it is completely dissolved, point 4 at the uniform velocity additions and virtue
Race's diamines molar ratio is 1:1 7.51kg 3,4,3', 4'- diphenyl thio-ether tetrformates dianhydride (3,4,3', 4'-TDPA), and with
Stir within 800r/ minutes, synthesize to obtain solid content M=10kg through polycondensation reaction 8h, i.e. solid content ratio is the polyamide of 20wt%
Acid resin solution；
IIth, prepared by black paste
The 2wt% of the solid content M in polyamic acid resin solution as obtained by step I takes nigrosine 0.2kg to add solvent
In N, N'- dimethyl-N, N'- acrylic urea (DMPU) 0.64kg, it is mixed evenly to obtain the black of nigrosine content 30%
Slurry；0.4 μm of this example nigrosine average grain diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 8wt% of the solid content M in polyamic acid resin solution as obtained by step I takes TITANIUM DIOXIDE DELUSTRANT 0.8kg
It is mixed evenly to obtain content of titanium dioxide ratio 30% after adding in solvent N, N'- dimethylformamide (DMF) 1.86kg
Delustring agent dispersing liquid, this example titanium dioxide average grain diameter be 0.05 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by delustring black polyamide thin film
By extrusion molding mould coated on ring steel belt, thickness is black polyamic acid solution prepared by step IV
400 μm, the dry solvent for removing 50wt% at 200 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamides
Amino acid film is peeled off and is delivered to from ring steel belt carries out 1 times of stretching in length and breadth on biaxial orientation stretching machine, at 250 DEG C of high temperature imidizations
Reason, this example carry out film the high temperature that temperature is 650 DEG C, the duration is 10s and are surface-treated after imidization processing；
The draw ratio that film is in tensioning state when high temperature is surface-treated is 1.Hereafter 220 DEG C of sizings are carried out, finally, winding, is made thickness
The delustring black polyamide thin film of 40 μm of degree.
Embodiment 6
Ith, the preparation of polyamic acid resin solution
In argon gas atmosphere, synthetic system temperature is controlled as 72 DEG C, to 40kg N, N'- dimethylacetylamides (DMAC) solvent
Middle addition 4.79kg aromatic diamines 4,4'- diaminodiphenyl ethers (4,4'-ODA) are stirred dissolving, and 4,4'-ODA are completely dissolved
Afterwards, it is 1 to divide 8 at the uniform velocity addition and aromatic diamine molar ratios:1 5.21kg aromatic dianhydride Pyromellitic Acid diacid (PMDA),
And stirred with 800r/ minutes, synthesize to obtain solid content M=10kg through polycondensation reaction 12h, i.e. solid content ratio is the poly- of 20wt%
Amic acid resin solution；
IIth, prepared by black paste
The 10wt% of the solid content M in polyamic acid resin solution as obtained by step I takes graphite 1kg to add solvent N,
It is mixed evenly to obtain the black paste of content of graphite 30% in N'- dimethylacetylamides (DMAC) 2.33kg；This example graphite
0.015 μm of average grain diameter.
The mixing added in this example solvent after black pigment is similar to Example 1.
IIIth, prepared by delustring agent dispersing liquid
The 12wt% of the solid content M in polyamic acid resin solution as obtained by step I cancels photo etching polyimides 1.2kg
It is mixed evenly to obtain polyimide content ratio 30% after adding in solvent N, N'- dimethylacetylamide (DMAC) 2.8kg
Delustring agent dispersing liquid, this example polyimides average grain diameter be 0.6 μm.
The mixing added in this example solvent after delustering agent is similar to Example 1.
IVth, prepared by black polyamic acid resin solution
Preparing for this step black polyamic acid resin solution is same as Example 1.
Vth, prepared by delustring black polyamide thin film
By extrusion molding mould coated on ring steel belt, thickness is black polyamic acid solution prepared by step IV
100 μm, the dry solvent for removing 80wt% at 220 DEG C, obtain with can self-supporting polyamide acid film.By gained polyamides
Amino acid film is peeled off and is delivered to from ring steel belt carries out 2 times of stretchings in length and breadth on biaxial orientation stretching machine, at 300 DEG C of high temperature imidizations
Reason, this example carry out film the high temperature that temperature is 660 DEG C, the duration is 90s and are surface-treated after imidization processing；
The draw ratio that film is in tensioning state when high temperature is surface-treated is 1.6.260 DEG C of sizings are carried out afterwards, are finally wound, and thickness is made
The delustring black polyamide thin film of 10 μm of degree.
Comparative example is 1.
Step I to IV same as Example 1,
When prepared by step V delustring black polyamide thin film, the surface treatment of no high temperature, only according to conventional filming technology into
Delustring black polyamide thin film is made in row stretching, imidization, heat treatment.
Comparative example is 2.
It is step I, II and step IV, V same as Example 1,
When prepared by step III delustring agent dispersing liquid, the average grain diameter of delustering agent silica is 2 μm, more than 1 μm.Still by step
The 2wt% of solid content M in the polyamic acid resin solution of rapid I gained takes 0.1kg silica to add solvent N, N'- dimethyl
It is mixed evenly to obtain the delustring agent dispersing liquid of dioxide-containing silica ratio 20% after in acetamide (DMAC) 0.5kg.
Comparative example is 3.
It is step I, II and step IV, V same as Example 1,
When prepared by step III delustring agent dispersing liquid, the average grain diameter of delustering agent silica is 0.008 μm, less than 0.01 μ
m。
Other preparation methods are identical with 1 step III of embodiment.
Comparative example is 4.
It is step I, III and step IV, V same as Example 1,
When prepared by step II black paste, 1.8 μm of carbon black average grain diameter, the black pigment more than application claims is averaged grain
0.8 μm of the footpath upper limit.
Other preparation methods are identical with 1 step II of embodiment.
Comparative example is 5.
It is step I, III and step IV, V same as Example 1,
When prepared by step II black paste, 0.008 μm of carbon black average grain diameter, the black pigment less than application claims is averaged
0.01 μm of particle diameter limit.
Other preparation methods are identical with 1 step II of embodiment.
Comparative example is 6.
Step I to IV same as Example 1,
When prepared by step V delustring black polyamide thin film, it is to temperature of film progress after imidization processing
900 DEG C, the high temperature that the duration is 2s surface treatment.
Other preparation methods are identical with 1 step V of embodiment.
Comparative example is 7.
Step I to IV same as Example 1,
When prepared by step V delustring black polyamide thin film, it is to temperature of film progress after imidization processing
600 DEG C, the high temperature that the duration is 150s surface treatment.
Other preparation methods are identical with 1 step V of embodiment.
It is swollen to detect the light transmittance of black polyamide thin film made from the various embodiments described above and each comparative example, glossiness, heat
Swollen coefficient (CTE), tensile strength, elongation, modulus, tearing strength and show the performances such as quality, the results are shown in Table 1：
1 embodiment of the present invention of table and the performance table of comparisons of film obtained by comparative example
As shown in table 1, embodiment 1 to 6 prepare delustring black polyamide thin film have relatively low glossiness, thoroughly
The excellent optical property such as light rate and mechanical property (tensile strength, elongation and modulus are of a relatively high), while also show height
Resistance to tearing (tearing strength) and good thermal property (such as CTE, shrinking percentage is relatively low).
Black polyamide thin film without the 1. middle preparation of the comparative example by high temperature surface treatment is without desired
Optical property, thermal property and mechanical property.Comparative example is 2. in 5., the average grain diameter of used black pigment and delustering agent
Excessive or too small, the black polyamide thin film optical property of preparation, thermal property and mechanical property are substantially poor.Comparative example is 6.
In, though cause film carbonization damage can not continuous film forming by high temperature surface treatment treatment temperature is excessive.Comparative example 7. in,
Though by high temperature surface treatment but treatment temperature is too low so that the reunion of the filler such as film surface delustering agent, black pigment is unknown
It is aobvious, so as to cause film glossiness higher.
Above-described embodiment, is only further described the purpose of the present invention, technical solution and beneficial effect specific
A example, the present invention are not limited to this.All any modifications made within the scope of disclosure of the invention, equivalent substitution, change
Into etc., it is all contained within protection scope of the present invention.
Claims (10)
1. a kind of delustring black polyamide thin film preparation method, including following key step:
Ith, the preparation of polyamic acid resin solution
Polyamic acid resin solution is prepared according to a conventional method, and in an inert atmosphere, it is 12 DEG C~75 DEG C to control synthetic system temperature
Under conditions of add aromatic diamine into solvent and be stirred dissolving, after aromatic diamine is completely dissolved, divides and at the uniform velocity add for 3~8 times
It is (0.9~1.1) with aromatic diamine molar ratio：1 aromatic dianhydride, and stirred with 120r/ minutes~1200r/ minutes, through contracting
3~24h of poly- reaction synthesizes to obtain polyamic acid resin solution；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
In the polyamic acid resin solution that the dosage control of the aromatic diamine, aromatic dianhydride and solvent is formed for this step
The ratio of solid content M is 10wt%~50wt%；
The aromatic diamine is 3,4'- diaminodiphenyl ethers, 1,3- bis--(4- amino-benzene oxygens) benzene, 4,4'- diaminourea hexichol
Any one in ether, 1,3- diaminobenzenes, 2,2'- bis- (trifluoromethyl) benzidine, 4,4'- benzidines and p-phenylenediamine
Or any a variety of combination；
The aromatic dianhydride is Pyromellitic Acid diacid, 3,3', and 4,4'- biphenyl four completes acid diacid acid anhydride, 2,2', 3,3'- biphenyl
Four, which complete acid diacid acid anhydride, diphenyl ether tetraformic dicarboxylic anhydride, Benzophenone, completes double (the 3,4- dicarboxylic acids phenyl) hexafluoros third of acid diacid acid anhydride, 2,2-
Alkane dianhydride, 4,4'- oxygen double phthalic anhydride, 3,4,3', 4'- diphenyl thio-ether tetrformates dianhydride, 2,3,2', 3'- diphenyl sulfides
Any one in tetracarboxylic acid dianhydride and 2,3,3', 4'- diphenyl thio-ether tetrformate dianhydride or any a variety of combination；
IIth, prepared by black paste
Take black pigment to add in solvent to be mixed evenly to obtain black paste；The amount of black pigment is added as described in step I
2wt%~20wt% of solid content M in polyamic acid resin solution, 0.01~0.8 μm of the black pigment average grain diameter；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
The solvent dosage control of the black paste is that the black pigment content ratio in black paste is 10wt%~30wt%；
IIIth, prepared by delustring agent dispersing liquid
Cancel after photo etching is added in solvent and be mixed evenly to obtain delustring agent dispersing liquid, the delustring dosage of addition is step I institute
2wt%~20wt% of the solid content M in polyamic acid resin solution is stated, the delustering agent average grain diameter is 0.01 μm~0.8 μ
m；
The solvent is aprotic polar solvent low molecular weight Carboxylamide, specially N, N'- dimethylacetylamides, N, N'-
Dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, tetramethyl sulfone, N, N'- dimethyl-N, N'- acrylic urea, N, N bis-
Any one in alkyl carboxyl acid amides or any a variety of combination；
The delustering agent is any one or any a variety of group in silica, polyimides, aluminium oxide and titanium dioxide
Close；
The solvent dosage control of the delustring agent dispersing liquid be dulling agent content ratio in delustring agent dispersing liquid be 10wt%~
30wt%；
IVth, prepared by black polyamic acid resin solution
Polyamic acid resin solution obtained by step I, black paste obtained by step II and the delustering agent obtained by step III is taken to disperse
Liquid blending and stirring, is made black polyamic acid resin solution, and defoams spare；
Vth, prepared by delustring black polyamide thin film
Black polyamic acid solution prepared by step IV by extrusion molding mould coated on ring steel belt, thickness for 20 μm~
520 μm, the then dry solvent for removing 85wt%~40wt% at 100~250 DEG C, obtain with can self-supporting polyamides
Amino acid film, gained polyamide acid film is peeled off from ring steel belt and is delivered to 0.8~2.2 times of progress on biaxial orientation stretching machine in length and breadth
Stretching, 180 DEG C~500 DEG C high temperature imidization processing, after last 180 DEG C~360 DEG C sizings, winding, is made thickness 2.5 μm~50
μm delustring black polyamide thin film；
After biaxial tension, either after imidization processing or after sizing, it is 640 DEG C~800 that a temperature is carried out to film
DEG C, the duration be 5s~120s high temperature be surface-treated.
2. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
The amount that the black pigment that black paste is added is prepared in the step II is 6wt%~10wt% of M.
3. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
Prepared in the step II average grain diameter of the black pigment that black paste is added O.02 μm~0.1 μm.
4. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
8wt%~12wt% that the amount that the step III prepares the delustering agent entered added by delustring agent dispersing liquid is M.
5. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
The step III prepare enter added by delustring agent dispersing liquid the average grain diameter of delustering agent for O.05 μm~0.6 μm.
6. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
The step III prepare enter added by delustring agent dispersing liquid the average grain diameter of delustering agent for O.08 μm~0.3 μm.
7. delustring black polyamide thin film preparation method according to any one of claim 1 to 6, it is characterised in that：
The step I prepares polyamic acid resin solution, step II prepares black paste and step III prepares delustering agent and disperses
Solvent used in liquid is identical.
8. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
The step V prepare the temperature of the high temperature surface treatment during delustring black polyamide thin film for 650 DEG C~
750 DEG C, the time is 10s~90s.
9. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
The step V prepare the temperature of the high temperature surface treatment during delustring black polyamide thin film for 660 DEG C~
700 DEG C, the time is 15s~60s.
10. delustring black polyamide thin film preparation method according to claim 1, it is characterised in that：
Film is in tensioning shape during the high temperature surface treatment during the step V preparation delustring black polyamide thin film
State, tensioning draw ratio are 1.0~1.6.
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